EP0222409A2 - Vulcanizable elastomeric compositions of fluoroelastomers - Google Patents
Vulcanizable elastomeric compositions of fluoroelastomers Download PDFInfo
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- EP0222409A2 EP0222409A2 EP86115817A EP86115817A EP0222409A2 EP 0222409 A2 EP0222409 A2 EP 0222409A2 EP 86115817 A EP86115817 A EP 86115817A EP 86115817 A EP86115817 A EP 86115817A EP 0222409 A2 EP0222409 A2 EP 0222409A2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
Definitions
- This invention relates to new cross-linking agents of the class of dihydroxypolyfluoroethers and to the use thereof in the vulcanization of fluoroelastomers based on vinylidene fluoride.
- Vulcanized elastomers based on vinylidene fluoride copolymers in which vinylidene fluoride is copolymerized with one or more monomers containing an ethylenic unsaturation and at least one fluorine atom are well-known and are widely utilized in a range of applications which require an exceptional chemical stability towards solvents, lubricants, fuels, acids and analogous products, even at very high temperatures.
- vulcanized articles obtained from such elastomeric polymers are most suitably utilized as sealing gaskets in general, both in static and dynamic conditions, in the automotive, aeronautic, missile, naval, mechanical and chemical sectors and as protection for various supports by making them impermeable, for example, as protective clothes against aggressive chemical agents or as sheaths for electric cables which are exposed to strong heat radiation and, finally, as protective coatings of industrial containers.
- the vulcanizable compositions of fluoroelastomers based on vinylidene fluoride comprise:
- compositions are described in GB-A-1 356 344 and US-A- 3 876 654 and 4 259 463.
- cross-linking agents having the structure of bisphenols lends good stability to the fluoroelastomers towards heat treatment.This stability is, however, accompanied by elasticity properties which are not too favourable as regards compression set after thermal post-treatment.
- the preferred compositions as total balance of the vulcanizing properties of the fluoroelastomers based on vinylidene fluoride, are obtained by using the compounds belonging to the class of bisphenol, in particular bisphenol AF.
- cross-linking agents which are capable of improving the stability towards thermal post-treatment associated with a better permanent resistance to compression (low compression set values) and to extrusion.
- an object of the present invention are dihydroxypolyfluoroethers having a molecular weight ranging from 360 to 2000 inclusive, selected from those classes of compounds comprising the following oxyfluoroalkylene repeating units:
- the diols of the indicated classes may also be present as mixtures.
- Fluoropolyoxyalkylene diols belonging to class I are, in particular, selected from compounds having the following general formula: HZ-CF2O(C2F4O) m (CF2O) n CF2-ZH wherein Z is where D and E are the same or different and are selected from -H, -CH3 and -CF3, m and n are integers, m + n having a value of preferably 2 to 22, and the ratio m/n ranges from 0.5 to 1.5, the oxyfluoroalkylene units being statistically distributed along the chain.
- These compounds can, for example, be prepared according to the methods described in US-A-3 810 874.
- Fluorinated diols belonging to class II are, in particular, selected from the compounds having the following general formula: HZ-CF2-(C3F6O) r (C2F4O) s (CFXO) t -CF2-ZH in which X is -F or -CF3, r is an integer having a value of preferably 1 to 3, s is an integer having a value of preferably 1 to 7, t is an integer having a value of preferably 1 to 7 and Z is the same as defined above.
- such compounds may be prepared by photooxidation of mixtures of C3F6 and C2F4, and by subsequent conversion of the -COF end groups to groups containing the end group -OH, said conversion being carried out according to known methods described in US-A-3 847 978 and 3 810 874.
- Fluorinated diols belonging to class III are, in particular, selected from the compounds having the general formula: HZ-CF2CH2(OCF2CF2CH2) p -OR′ f O-(CH2CF2CF2O) q CH2CF2-ZH and described in EP-A-148 482, in which the -COF end groups can be converted to -OH end groups, as described in US-A-3 847 978 and 3 810 874, Z being the same as defined above and R′ f being a perfluoroalkylene group, in particular, -CF2-CF2-.
- Fluorinated diols belonging to class IV are, in particular,selected from the compounds having the general formula: wherein A is a group comprising the end group -OH, for example, CH2OH, and n is an integer equal to or greater than 1.
- the fluoroelastomers forming component (A) are, generally, copolymers of vinylidene fluoride and hexafluoropropene and, optionally, tetrafluoroethylene.
- chlorotrifluoroethylene 1-hydropentafluoropropene and 2-hydropentafluoropropene instead of hexafluoropropene.
- the tetrafluoroethylene and/or hexafluoropropene units in the copolymers may be partially or fully replaced by per fluoroalkylvinylether units.
- the amount of perfluoroalkylvinylether units generally ranges from 0.5 to 15 mole %, based on the total amount of copolymer. Preferably, it is lower than 5 mole%.
- fluorinated monomers may also be employed as comonomers, provided they contain an ethylene-type double bond and at least one fluorine atom.
- Compounds (A) may be prepared as described in the literature (Kirk-Othmer, Encyclopaedia of Chem. Technology, Vol. 8, pages 500 ff., 1979) by preferably operating in an aqueous emulsion and, optionally, in the presence of chain transfer agents like those described in US-A-4 000 356.
- copolymers in which the amount of vinylidene fluoride ranges from 40 to 85 mole%, the amount of perfluoropropene ranges from 15 to 30 mole% and the amount of tetrafluoroethylene ranges from 0 to 30 mole% are particularly preferred.
- Accelerator (B) belongs to the classes previously mentioned, the preferred compounds being: - From among the quaternary ammonium salts: methyltrioctylammonium chloride, laurylpyridinium bromide and benzyltrioctylammonium chloride; - From among the quaternary phosphonium salts: benzyltri phenylphosphonium chloride, benzyltriphenylphosphonium tetrafluoroborate, methyltrioctyphosphonium acetate and carbethoxymethyltriphenylphosphonium bromide; - From among the phosphoranamine derivatives or aminophosphonium compounds: 1-chloro - 1-benzyl - 1,1-diphenyl-N-(diethyl)phosphoranamine; 1-tetrafluoroborate - 1-benzyl-N,N′N"-(hexamethyl)phosphorantriamine; 1-bromo - 1-benzy
- Component (C) is an inorganic compound such as an oxide of a divalent metal, for example, ZnO, MgO, PbO, CaO or a mixture of the oxides and hydroxides of said metals or a salt of a weak acid, as is described in US-A-3 876 654.
- a divalent metal for example, ZnO, MgO, PbO, CaO or a mixture of the oxides and hydroxides of said metals or a salt of a weak acid, as is described in US-A-3 876 654.
- Compound (D) is a dihydroxypolyfluoroether as defined above.
- an elastomeric copolymer of vinylidene fluoride (A) and one or more fluorinated monomers as indicated above there are employed: - 1 to 40 parts by weight of basic acceptor (C) consisting of one or more oxides of divalent metals as specified above, optionally, in the form of cationic complexes or chelates, optionally, in the presence of 0 to 10 parts by weight of one or more basic compounds selected from the group comprising calcium, strontium and barium hydrates, metal salts of weak acids such as carbonates, benzoates, and phosphates of calcium, strontium, barium, sodium and potassium, optionally, in the form of complexes with the usual cationic chelating or complexing compounds of the type well known to those skilled in the art; - 1 to 15 parts by weight of dihydroxypolyfluoroether (D) as specified above; - 0.05 to 5 parts by weight of a vulcanization accelerator (B) selected from those classes described
- the vulcanizable compositions of the above-mentioned type are vulcanized by means of a process wherein said compositions are first heated under pressure at temperatures from 130 to 230°C, preferably from 160 to 200°C, for 0.5 to 60 minutes and, preferably, for 1 to 20 minutes.
- the resulting articles are then post-vulcanized in an oven or in a furnace, at atmospheric pressure, at temperatures from 130 to 315°C, preferably from 200 to 275°C, for 5 to 48 hours, preferably from 10 to 24 hours.
- Such articles exhibit an excellent stability towards permanent compression deformation, a very low tendency to scorching as function of the storage time and temperature or of the temperatures of particular processing technologies such as, for example, extrusion. They also exhibit a high stability with respect to thermal ageing. Furthermore, they can be bonded to various kinds of metallic substrates to which they firmly adhere, even at high temperatures.
- composition according to the invention may advantageously contain all kinds of fluorinated polymeric materials based on vinylidene fluoride of the elastomeric type, optionally, containing substituents other than fluorine and chlorine, and also mixtures of two or more fluorinated elastomers.
- the vulcanizable compositions according to the invention may, in addition to the aforesaid components (A) to (D), contain carbon black, white and coloured fillers, conventional plasticizers and lubricants such as stearates, aryl phosphates, polyethers, polyesters, polyethylene, sulphones, sulphoxides and other known additives, according to the techniques usually adopted by the users of fluorinated elastomers.
- the components of the vulcanizable compositions according to the present invention can readily be incorporated into the elastomeric copolymer of vinylidene fluoride, either individually or premixed.
- a further advantage of the present invention is the full elimination of the undesired phenomenon of "reduced mould shrinkage" of fluorinated elastomer articles, particularly in the case of O-ring gaskets, during vulcanization in a closed mould and under pressure.
- the mixture of phosphoranamine accelerator (B) (0.2 to 2 parts by weight) and of dihydroxypolyfluoroether cross-linking agent (D) (2 to 8 parts by weight) is added to the fluorinated elastomer (100 parts by weight) prior to the addition of the basic acceptor (2 to 10 parts by weight), of the basic compounds (1 to 7 parts by weight), of the reinforcing and inert fillers, the lubricants, the plasticizers and further optional additives.
- the vulcanized elastomers prepared from the compositions of the present invention may be utilized as sealing gaskets, both in static and dynamic conditions, in the automotive, mechanical and naval sectors, as protective clothes against aggressive chemical agents, as sheaths for the protection of electric cables when exposed to an intense thermal radiation and in analogous applications, as already mentioned.
- Fluoroelastomers CH2 CF2/C3F6 copolymer in a molar ratio of 4/1, having a specific weight of 1.8 at 25°C, known as Technoflon NM® (Montedison S.p.A.).
- Accelerator 1 1-chloro-1,1-diphenyl-1-benzyl - N-diethylphosphoranamine.
- Accelerator 2 Benzyltriphenylphosphonium chloride.
- Dihydroxypolyfluoropolyether 1 (cross-linking agent) of the formula HOCH2CF2(C2F4O) m (CF2O) n CF2CH2OH and having a mean molecular weight (based on the hydroxyl titre) of 40 and an m/n ratio of 0.9.
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Abstract
Description
- This invention relates to new cross-linking agents of the class of dihydroxypolyfluoroethers and to the use thereof in the vulcanization of fluoroelastomers based on vinylidene fluoride.
- Vulcanized elastomers based on vinylidene fluoride copolymers in which vinylidene fluoride is copolymerized with one or more monomers containing an ethylenic unsaturation and at least one fluorine atom are well-known and are widely utilized in a range of applications which require an exceptional chemical stability towards solvents, lubricants, fuels, acids and analogous products, even at very high temperatures.
- The vulcanized articles obtained from such elastomeric polymers are most suitably utilized as sealing gaskets in general, both in static and dynamic conditions, in the automotive, aeronautic, missile, naval, mechanical and chemical sectors and as protection for various supports by making them impermeable, for example, as protective clothes against aggressive chemical agents or as sheaths for electric cables which are exposed to strong heat radiation and, finally, as protective coatings of industrial containers.
- According to the most advanced prior art, the vulcanizable compositions of fluoroelastomers based on vinylidene fluoride comprise:
- (A) A copolymer of vinylidene fluoride with at least one other fluorinated monomer containing an ethylenic unsaturation;
- (B) A vulcanization accelerator selected from quaternary ammonium salts, quaternary phosphonium salts and phosphoranamine derivatives;
- (C) One or more basic acceptors (basic agents which are acceptors for acids) such as MgO and Ca(OH)₂;
- (D) A cross-linking agent having a bisphenol structure, for example, bisphenol AF.
- Examples of these compositions are described in GB-A-1 356 344 and US-A- 3 876 654 and 4 259 463.
- As compared with other cross-linking agents of the art, the use of cross-linking agents having the structure of bisphenols lends good stability to the fluoroelastomers towards heat treatment.This stability is, however, accompanied by elasticity properties which are not too favourable as regards compression set after thermal post-treatment.
- Furthermore, the use of other linear-chain cross-linking agents with hydroxyl end groups is known; see, for example, those described in US-A-4 188 352.
- Representative examples of these compounds are:
HOCH₂-(CF₂)₃-CH₂OH
HOCH₂-CF₂-CH₂(CF₂)₃-CFHCF₂CH₂OH - However, the preferred compositions, as total balance of the vulcanizing properties of the fluoroelastomers based on vinylidene fluoride, are obtained by using the compounds belonging to the class of bisphenol, in particular bisphenol AF.
- There was, thus, a great need for cross-linking agents which are capable of improving the stability towards thermal post-treatment associated with a better permanent resistance to compression (low compression set values) and to extrusion.
- It has now unexpectedly and surprisingly been found that, with the use of dihydroxypolyfluoroethers as cross-linking agent, a vulcanizate based on vinylidene fluoride having a better overall balance of the above-mentioned properties, even after a thermal post-treatment, is obtained.
- Thus, an object of the present invention are dihydroxypolyfluoroethers having a molecular weight ranging from 360 to 2000 inclusive, selected from those classes of compounds comprising the following oxyfluoroalkylene repeating units:
- I (C₂F₄O), (CF₂O), said units being statistically distributed along the fluoropolyoxyalkylene chain
- II (C₃F₆O), (C₂F₄O), (CFXO) ,wherein X is -F or -CF, said units being statistically distributed along the fluoropolyoxyalkylene chain,
- III - CH₂ - CF₂ - CF₂ - O-
said units being linked within the fluoropolyoxyalkylene chain in the following manner: -
- The diols of the indicated classes may also be present as mixtures.
- Fluoropolyoxyalkylene diols belonging to class I are, in particular, selected from compounds having the following general formula:
HZ-CF₂O(C₂F₄O)m(CF₂O)nCF₂-ZH
wherein Z is - Fluorinated diols belonging to class II are, in particular, selected from the compounds having the following general formula:
HZ-CF₂-(C₃F₆O)r(C₂F₄O)s(CFXO)t-CF₂-ZH
in which X is -F or -CF₃, r is an integer having a value of preferably 1 to 3, s is an integer having a value of preferably 1 to 7, t is an integer having a value of preferably 1 to 7 and Z is the same as defined above. - As described in US-A- 3 665 041 such compounds may be prepared by photooxidation of mixtures of C₃F₆ and C₂F₄, and by subsequent conversion of the -COF end groups to groups containing the end group -OH, said conversion being carried out according to known methods described in US-A-3 847 978 and 3 810 874.
- Fluorinated diols belonging to class III are, in particular, selected from the compounds having the general formula:
HZ-CF₂CH₂(OCF₂CF₂CH₂)p-OR′fO-(CH₂CF₂CF₂O)qCH₂CF₂-ZH
and described in EP-A-148 482, in which the -COF end groups can be converted to -OH end groups, as described in US-A-3 847 978 and 3 810 874, Z being the same as defined above and R′f being a perfluoroalkylene group, in particular, -CF₂-CF₂-. -
- Such compounds are described in EP-A-151 877.
- The fluoroelastomers forming component (A) are, generally, copolymers of vinylidene fluoride and hexafluoropropene and, optionally, tetrafluoroethylene.
- It is possible to use chlorotrifluoroethylene, 1-hydropentafluoropropene and 2-hydropentafluoropropene instead of hexafluoropropene.
- It is also possible to utilize mixtures of the above comonomers.
- The tetrafluoroethylene and/or hexafluoropropene units in the copolymers may be partially or fully replaced by per fluoroalkylvinylether units.
- The amount of perfluoroalkylvinylether units generally ranges from 0.5 to 15 mole %, based on the total amount of copolymer. Preferably, it is lower than 5 mole%.
- Other fluorinated monomers may also be employed as comonomers, provided they contain an ethylene-type double bond and at least one fluorine atom.
- Compounds (A) may be prepared as described in the literature (Kirk-Othmer, Encyclopaedia of Chem. Technology, Vol. 8, pages 500 ff., 1979) by preferably operating in an aqueous emulsion and, optionally, in the presence of chain transfer agents like those described in US-A-4 000 356.
- The copolymers in which the amount of vinylidene fluoride ranges from 40 to 85 mole%, the amount of perfluoropropene ranges from 15 to 30 mole% and the amount of tetrafluoroethylene ranges from 0 to 30 mole% are particularly preferred.
- Accelerator (B) belongs to the classes previously mentioned, the preferred compounds being:
- From among the quaternary ammonium salts: methyltrioctylammonium chloride, laurylpyridinium bromide and benzyltrioctylammonium chloride;
- From among the quaternary phosphonium salts: benzyltri phenylphosphonium chloride, benzyltriphenylphosphonium tetrafluoroborate, methyltrioctyphosphonium acetate and carbethoxymethyltriphenylphosphonium bromide;
- From among the phosphoranamine derivatives or aminophosphonium compounds: 1-chloro - 1-benzyl - 1,1-diphenyl-N-(diethyl)phosphoranamine; 1-tetrafluoroborate - 1-benzyl-N,N′N"-(hexamethyl)phosphorantriamine; 1-bromo - 1-benzyl-1-phenyl-N,N′-(tetraethyl)phosphorandiamine. - Component (C) is an inorganic compound such as an oxide of a divalent metal, for example, ZnO, MgO, PbO, CaO or a mixture of the oxides and hydroxides of said metals or a salt of a weak acid, as is described in US-A-3 876 654.
- Compound (D) is a dihydroxypolyfluoroether as defined above.
- Generally, per 100 parts by weight of an elastomeric copolymer of vinylidene fluoride (A) and one or more fluorinated monomers as indicated above, there are employed:
- 1 to 40 parts by weight of basic acceptor (C) consisting of one or more oxides of divalent metals as specified above, optionally, in the form of cationic complexes or chelates, optionally, in the presence of 0 to 10 parts by weight of one or more basic compounds selected from the group comprising calcium, strontium and barium hydrates, metal salts of weak acids such as carbonates, benzoates, and phosphates of calcium, strontium, barium, sodium and potassium, optionally, in the form of complexes with the usual cationic chelating or complexing compounds of the type well known to those skilled in the art;
- 1 to 15 parts by weight of dihydroxypolyfluoroether (D) as specified above;
- 0.05 to 5 parts by weight of a vulcanization accelerator (B) selected from those classes described above. - The vulcanizable compositions of the above-mentioned type are vulcanized by means of a process wherein said compositions are first heated under pressure at temperatures from 130 to 230°C, preferably from 160 to 200°C, for 0.5 to 60 minutes and, preferably, for 1 to 20 minutes. The resulting articles are then post-vulcanized in an oven or in a furnace, at atmospheric pressure, at temperatures from 130 to 315°C, preferably from 200 to 275°C, for 5 to 48 hours, preferably from 10 to 24 hours.
- It has, surprisingly, been found that the vulcanizable compositions of the present invention, through extrusion moulding and subsequent vulcanization and also by utilizing highly automatized injection technology, can be transformed to articles of any shape and dimension. No drawbacks such as scorching or hot-tearing phenomena are encountered at the plastification temperatures usually employed for injection moulding.
- Such articles exhibit an excellent stability towards permanent compression deformation, a very low tendency to scorching as function of the storage time and temperature or of the temperatures of particular processing technologies such as, for example, extrusion. They also exhibit a high stability with respect to thermal ageing. Furthermore, they can be bonded to various kinds of metallic substrates to which they firmly adhere, even at high temperatures.
- It has also been observed that the vulcanizable compositions comprising components (A) to (D) described above do not stick to the moulds or soil them so that there are practically no production rejections. Thus, high production standards and extremely regular processing cycles are attained.
- More generally, the composition according to the invention may advantageously contain all kinds of fluorinated polymeric materials based on vinylidene fluoride of the elastomeric type, optionally, containing substituents other than fluorine and chlorine, and also mixtures of two or more fluorinated elastomers.
- The vulcanizable compositions according to the invention may, in addition to the aforesaid components (A) to (D), contain carbon black, white and coloured fillers, conventional plasticizers and lubricants such as stearates, aryl phosphates, polyethers, polyesters, polyethylene, sulphones, sulphoxides and other known additives, according to the techniques usually adopted by the users of fluorinated elastomers.
- The components of the vulcanizable compositions according to the present invention can readily be incorporated into the elastomeric copolymer of vinylidene fluoride, either individually or premixed.
- In this way it is possible to achieve good vulcanization rates at the usual processing temperatures without any risk of scorching (prevulcanization) during the initial processing steps which precede the actual vulcanization.
- A further advantage of the present invention is the full elimination of the undesired phenomenon of "reduced mould shrinkage" of fluorinated elastomer articles, particularly in the case of O-ring gaskets, during vulcanization in a closed mould and under pressure.
- In a preferred embodiment of the present invention the mixture of phosphoranamine accelerator (B) (0.2 to 2 parts by weight) and of dihydroxypolyfluoroether cross-linking agent (D) (2 to 8 parts by weight) is added to the fluorinated elastomer (100 parts by weight) prior to the addition of the basic acceptor (2 to 10 parts by weight), of the basic compounds (1 to 7 parts by weight), of the reinforcing and inert fillers, the lubricants, the plasticizers and further optional additives.
- By operating in this way, it is possible to achieve a prompt, controllable and uniform vulcanization without giving rise to undesired phenomena such as scorching during the various processing steps of the mixture or during its storage.
- The vulcanized elastomers prepared from the compositions of the present invention may be utilized as sealing gaskets, both in static and dynamic conditions, in the automotive, mechanical and naval sectors, as protective clothes against aggressive chemical agents, as sheaths for the protection of electric cables when exposed to an intense thermal radiation and in analogous applications, as already mentioned.
- The following examples merely serve to illustrate the invention and do not limit it in any way.
- In the examples reported in table 1 the following products were used:
- Fluoroelastomers CH₂ = CF₂/C₃F₆ copolymer in a molar ratio of 4/1, having a specific weight of 1.8 at 25°C, known as Technoflon NM® (Montedison S.p.A.).
- Accelerator 1 1-chloro-1,1-diphenyl-1-benzyl - N-diethylphosphoranamine.
- Accelerator 2 Benzyltriphenylphosphonium chloride.
- Dihydroxypolyfluoropolyether 1 (cross-linking agent) of the formula HOCH₂CF₂(C₂F₄O)m(CF₂O)nCF₂CH₂OH and having a mean molecular weight (based on the hydroxyl titre) of 40 and an m/n ratio of 0.9.
- Dihydroxypolyfluoropolyether 2 of the same general formula as the preceding polyether but having an average molecular weight of 800.
- The results of the tests reported in table 1 show that the compositions of the invention lead to better compression set values, to an improvement of the heat stability proper ties after ageing at 270°C and to an improvement of the extrudability when compared with the values obtained in comparative example 1, wherein bisphenol AF is utilized as a cross-linking agent.
Claims (7)
said units being linked within the fluoropolyoxyalkylene chain in the following manner:
-(O-CF₂-CF₂-CH₂)p-O-R′f-O(-CH₂-CF₂-CF₂-O)q-
wherein R′f is a fluoroalkylene group and p and q are integers;
HZ-CF₂O(C₂F₄O)m(CF₂O)nCF₂-ZH
wherein Z is
HZ-CF₂-(C₃F₆O)r(C₂F₄O)s(CFXO)t-CF₂-ZH
in which X is -F or -CF₃, r is an integer having a value of preferably 1 to 3, s is an integer having a value of preferably 1 to 7, t is an integer having a value of preferably 1 to 7 and Z is as defined in claim 2.
HZ-CF₂CH₂(OCF₂CF₂CH₂)p-OR′fO-(CH₂CF₂CF₂O)qCH₂CF₂-ZH
where Z is as defined in claim 2.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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IT2286485 | 1985-11-15 | ||
IT22864/85A IT1188202B (en) | 1985-11-15 | 1985-11-15 | VULCANIZABLE ELASTOMERIC COMPOSITIONS OF FLUOROELASTOMERS |
Publications (3)
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EP0222409A2 true EP0222409A2 (en) | 1987-05-20 |
EP0222409A3 EP0222409A3 (en) | 1989-02-22 |
EP0222409B1 EP0222409B1 (en) | 1992-02-12 |
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EP86115817A Expired EP0222409B1 (en) | 1985-11-15 | 1986-11-14 | Vulcanizable elastomeric compositions of fluoroelastomers |
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US (1) | US4810760A (en) |
EP (1) | EP0222409B1 (en) |
JP (1) | JP2527946B2 (en) |
DE (1) | DE3683889D1 (en) |
IT (1) | IT1188202B (en) |
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IT1190352B (en) * | 1985-04-05 | 1988-02-16 | Montefluos Spa | PROCEDURE FOR THE PRODUCTION OF A COMPOSITE MATERIAL BASED ON A POLYMER MATRIX |
US4977222A (en) * | 1987-03-16 | 1990-12-11 | Ausimont S.P.A. | Cross-linking of thermosetting resins by means of heating with saturated perfluoropolyether vapor in the presence of a secondary fluid |
US5266650A (en) * | 1990-10-11 | 1993-11-30 | Minnesota Mining And Manufacturing Company | Curing fluorocarbon elastomers |
US5384374A (en) * | 1991-01-11 | 1995-01-24 | Minnesota Mining And Manufacturing Company | Curing fluorocarbon elastomers |
JP3240758B2 (en) * | 1993-07-15 | 2001-12-25 | ミノルタ株式会社 | Zoom lens device and camera |
US5668203A (en) * | 1995-06-07 | 1997-09-16 | Xerox Corporation | Elastomeric articles containing haloceramer compositions |
US5681881A (en) * | 1996-05-24 | 1997-10-28 | Minnesota Mining And Manufacturing Company | Fluoroelastomer compositions |
IT1286042B1 (en) * | 1996-10-25 | 1998-07-07 | Ausimont Spa | O-RINGS FROM VULCANIZABLE FLUOROELASTOMERS BY IONIC WAY |
US5728773A (en) * | 1997-02-21 | 1998-03-17 | Minnesota Mining And Manufacturing Company | Fluoroelastomer composition with organo-onium and blocked-carbonate compounds |
US6239223B1 (en) | 1997-09-05 | 2001-05-29 | Chemfab Corporation | Fluoropolymeric composition |
DE60036560T2 (en) * | 1999-10-12 | 2008-06-19 | Entegris, Inc., Chaska | FLUORO CARBON POLYMER COMPOSITIONS WITH HYDROPHILIC FUNCTIONAL GROUPS AND METHOD FOR THE PRODUCTION THEREOF |
ITMI20020598A1 (en) | 2002-03-22 | 2003-09-22 | Ausimont Spa | VULCANIZABLE FLUOROELASTOMERS |
ITMI20040830A1 (en) * | 2004-04-27 | 2004-07-27 | Solvay Solexis Spa | VULCANIZABLE FLUOROELASTOMERS |
WO2017102818A1 (en) * | 2015-12-14 | 2017-06-22 | Solvay Specialty Polymers Italy S.P.A. | Fluoroelastomer compositions |
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GB1356344A (en) * | 1970-05-20 | 1974-06-12 | Du Pont | Curable fluoroelastomer compositions and a process for curing said compositions |
FR2413426A1 (en) * | 1977-12-30 | 1979-07-27 | Daikin Ind Ltd | ELASTOMERIC COMPOSITION BASED ON FLUORINE ELASTOMER AND EPICHLORHYDRIN ELASTOMER |
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US3845051A (en) * | 1970-09-08 | 1974-10-29 | Minnesota Mining & Mfg | Alpha,omega-di-s-triazinyl perfluoropolyoxa-alkanes |
JPS5923578B2 (en) * | 1978-05-01 | 1984-06-02 | ダイキン工業株式会社 | Fluoro rubber composition |
US4358559A (en) * | 1981-11-19 | 1982-11-09 | Minnesota Mining And Manufacturing Company | Tacky fluoroelastomer compositions |
JPH0234888B2 (en) * | 1982-08-12 | 1990-08-07 | Kagaku Gijutsucho Mukizaishitsu Kenkyushocho | SENIJOCHITANSANKARIUMUNOSEIZOHO |
JPS59217749A (en) * | 1983-05-24 | 1984-12-07 | Asahi Chem Ind Co Ltd | Fluorine-containing elastomer composition |
US4647413A (en) * | 1983-12-27 | 1987-03-03 | Minnesota Mining And Manufacturing Company | Perfluoropolyether oligomers and polymers |
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1985
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- 1986-11-10 JP JP61265730A patent/JP2527946B2/en not_active Expired - Fee Related
- 1986-11-10 US US06/928,403 patent/US4810760A/en not_active Expired - Lifetime
- 1986-11-14 DE DE8686115817T patent/DE3683889D1/en not_active Expired - Fee Related
- 1986-11-14 EP EP86115817A patent/EP0222409B1/en not_active Expired
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GB1356344A (en) * | 1970-05-20 | 1974-06-12 | Du Pont | Curable fluoroelastomer compositions and a process for curing said compositions |
FR2413426A1 (en) * | 1977-12-30 | 1979-07-27 | Daikin Ind Ltd | ELASTOMERIC COMPOSITION BASED ON FLUORINE ELASTOMER AND EPICHLORHYDRIN ELASTOMER |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0805180A1 (en) * | 1996-05-02 | 1997-11-05 | AUSIMONT S.p.A. | Curable compositions of fluoroelastomers |
US6005054A (en) * | 1996-05-02 | 1999-12-21 | Austimont S.P.A. | Curable composition of fluoroelastomers |
US10358551B2 (en) | 2010-07-20 | 2019-07-23 | Solvay Specialty Polymers Italy S.P.A. | Fluoroelastomer composition |
WO2020044188A1 (en) * | 2018-08-27 | 2020-03-05 | 3M Innovative Properties Company | Peroxide curable highly fluorinated polymers comprising an internal fluorinated plasticizer and articles therefrom |
Also Published As
Publication number | Publication date |
---|---|
JP2527946B2 (en) | 1996-08-28 |
JPS62119252A (en) | 1987-05-30 |
IT1188202B (en) | 1988-01-07 |
EP0222409A3 (en) | 1989-02-22 |
US4810760A (en) | 1989-03-07 |
EP0222409B1 (en) | 1992-02-12 |
IT8522864A0 (en) | 1985-11-15 |
DE3683889D1 (en) | 1992-03-26 |
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